Aminomethyleneiminophenyl carbamates



United States Patent Oflice 3,542,853 Patented Nov. 24, 1970 Int. Cl. C07c 131/00 US. Cl. 260479 10 Claims ABSTRACT OF THE DISCLOSURE Pesticidal phenyl-carbamate derivatives.

This invention relates to pesticides, and more particularly to novel canbamate derivatives which have insecti cidal and acaricidal effects.

This application is a division of pending application Ser. No. 290,586, filed June 26, 1963, now Pat. No. 3,336,186.

We have found that compounds of the formula wherein R is lower alkyl or cyclohexyl; R and R are lower alkyl or jointly constitute a divalent radical which forms a fiveand six-member heterocyclic ring with the associated N atom containing in addition to said N atom only C atoms or an O atom and C atoms; R; and R are hydrogen, lower alkyl, lower alkenyl, or halogen; are efiective agents for combatting insect pests and spider mites which are plant parasites. The compounds of the invention and their salts with any suitable acid are capable of surprisingly long action when incorporated in pesticidal compositions. 1

Such compositions are highly effective against a broad spectrum of pest insects. They may be employed to advantage where it is necessary to combat acarids and insects simultaneously, for example, in orchards, vineyards, truck gardens, and hop field's, in cotton crops, and in other crops in which insects may occur simultaneously with spider mites.

The compounds of the invention may be employed against pests in their pure form, in mixtures with each other and with other pest control agents such as acaricidal, insecticidal, or fungicidal compounds. They may constitute the active agents of compositions of all types commonly employed for the protection of crops against pests. Such compositions, in addition to the active agents, may contain liquid or solid inert carriers. Suitable liquid carriers include water, mineral oil, and other solvents. Solid inert carriers include bentonite, fullers earth, gypsum, limestone, diatomaceous earth, pyrophillite, silicon dioxide in its various natural forms, talcum, and powders of vegetal origin such as cotton seed flour or nut shell flour. The composition may contain conventional auxiliary agents such as emulsifiers, wetting agents, binders, stabilizers, propellent gases, perfumes, pest attracting and pest repelling agents. The composition may be applied by dusting or otherwise spreading when they are solid. When liquid, they may be applied by fogging, spraying, or atomizing. The liquid compositions may be suspensions, emulsions, or solutions of the active agents, and may also be applied in the form of aerosols of fumigants.

The percentage of active agents in the compositions may be varied within wide limits. The concentration selected will depend on the type of composition, the method of application, the desired pesticidal eifect, and particularly on the type of pest to be controlled. The content of active agents in the compositions of the invention will usually vary between 0.1 and percent by weight. The compositions are generally applied in concentrations between 0.025 and 10 percent. Under exceptional conditions, it may be necessary to apply them in concentrations as high as 20 percent. 7

Representative carbamate derivatives of the invention which have excellent insecticidal and acaricidal eifects are listed in Table 1 together with identifying physical properties. Where the formula of an acid radical appears in conjunction with the name of its saltin Table 1, it will be understood that the compound is characterized by the melting point of its salt.

(chloracctate) xxv-..- Q-o-b-NH-on,

Oil n =1.5450.

MI. 125 C.

- EXAMPLE 1 Bush beans (Phaseolus vulgaris L.) infested with spider mites of the species Tetranychus urticae KOCH in all stages of development were treated in the late twoleaf stage with aqueous suspensions and emulsions or solutions of salts of active agents of the invention in various concentrations. The compositions were applied by spraying from a spray gun having a glass nozzle at a pressure of 0.5 kg./ cm. gauge while the potted plants were moving on a rotating table. The amount of liquid applied was 50 milliliters, and ensured wetting of the three plants contained in each pot until excess liquid dripped from them. The mortality of the postembryonal stages of the parasites after seven days was recorded in percent of the parasites present. The results are listed in Table 2.

TABLE 2 Mortality Concentration of adults Mortal ty of active and of emerging Compound number agent, percent nymphs, larvae, percent percent I 0. 1 100 100 P2 133 I (lactate) 0965 180 100 1 I 00 100 I (hyd 9 09 5 ion 0 100 I (dihydrogenphosphate) 9 $8 100 II 0. 1 100 100 0. 1 100 100 0. O5 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 100 0. 5 100 100 0. 1 100 100 0. O5 80 80 0. 1 80 80 0. 1 100 100 0. 1 80 50 0. 1 100 100 0. 1 100 100 0. 1 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 100 0. 05 100 100 0. 1 100 80 0. 05 100 50 0. 1 90 90 0. 1 100 100 0. 05 100 100 EXAMPLE 2 The residual eflfect of representative compounds of the invention was determined by treating bush bean plants in the late two leaf stage as described in Example 1. Other potted plants were infected for the first time 24 hours after treatment of the first group of plants and again at intervals of two to four days by placing spider mite infected leaves of the first group on leaves of the healthy plants. The mortality of the spider mites on the second group of plants seven days after infection by the applied leaves are tabulated in Table 3.

TABLE 3 Residual effect on postembryonal Concentration stages after number days Compound of active agent, number percent 1 3 6 8 10 16 I 0. 01 100 100 100 100 90 0. 005 100 100 90 40 In 0. 01 100 100 95 100 100 95 0. 005 100 100 100 60 80 80 VII 0. 01 100 100 100 100 100 100 EXAMPLE 3 The roots (a) or the stalks (b) of cut branches of bush bean plants free from parasites were placed in aqueous emulsions or salt solutions of several representative compounds of the invention when the plants were in the twoleaf stage. They were then infected by contact with leaves carrying spider mites, and a count of surviving parasites 48 hours after infestation gave the results listed in Table 4.

TABLE 4 Mortality of post Concentration postembryonal of active agent, stages after seven Bush bean seeds were placed in recesses of clay dishes, and the recesses were treated with solid mixtures of two parts of representative active agents of the invention and 98 parts kaolin. No unfavorable effects of the compounds of the invention could be observed in comparison tests between the treated seeds and untreated controls with respect to germination and growth. When the plants had reached the two-leaf stage, they were infected with 7 moving spider mites in all postembryonal stages by application of leaves from infected plants. The mortality of the mites was determined after seven days, and the results obtained are listed in Table 5.

TABLE Grams active Mortality of postagent per 100 g. embryonal stages.

Glass plates were treated with aqueous emulsions or solutions of salts of the compounds of the invention in various concentrations. The liquid compositions were applied in amounts of 4 milligrams per square centimeter by means of a spray gun having a glass nozzle at a pressure of 0.5 kilogram per square centimeter. The liquid coatings were permitted to dry, and the plates were placed as top covers on glass cylinders each containing 20 house flies (Musca domestica L.), four days old. The flies were fed during the experiments with an untreated solution of sugar.

The effects of the compounds on the flies after twenty hours exposure were determined by counting the dead flies, the flies recognizably damaged and lying on their backs, and the flies surviving without visible symptoms. The percentage effect of the various compounds of the invention was calculated according to Abbotts method. The results obtained are listed in Table 6.

95 5 99999999 NHNHMNNNHNN EXAMPLE 6 The bottoms of Petri dishes were treated with various concentrations of compounds of the invention in aqueous emulsions or as solutions of their salts at a dosage of 4 milligrams per square centimeter. After drying of the liquid coatings, the dishes were stocked each with approximately 100 granary weevils (Sitophilus granarius L.).

After 24 hours exposure of the insects in a dark room in the open dishes, a ditferential count was made of weevils surviving without symptoms, dead weevils, and damaged weevils lying on their backs. The percentage effect was calculated according to Abbotts method, and the results are listed in Table 7.

TABLE 7 Concentration of Percentage efiect active agent, after 24 hours percent exposure Compound number H .3 H H I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I o o co cc 0 XV XVII (p-toluolsullonate) XXV EXAMPLE 7 The stomach and contact effects of the insecticidal compounds of the invention was determined by treating shoots of tradescantia on a revolving turntable with aqueous emulsions, suspensions, or salt solutions of the compounds of the invention in amounts of 4 mg./cm. After drying of the sprayed coatings, the treated plants were each stocked in a wire gauze cage with 15 fourth-stage larvae of stick insects (Carausius morosus Brunner) which had recently shed their skins. The elfects of the compounds on the animals were evaluated daily by separate counts of dead animals, severely damaged animals which reacted to contact only by uncoordinated movement of the extremities, slightly damaged animals, and normal animals. The results of the test are listed in Table 8.

TABLE 8 Concentration of active agent, percent Percentage ell'ect after I 0 0? I (hydrochloride) 0 b5 0 1 05 .l. 05

I (lactate) 0 I (dihydrogen-phosphate) EXAMPLE 8 TABLE 9 Percentage effect after number days on plants stocked Compound number 3 6 9 14 21 28 28 plus III 100 100 100 100 100 100 100 VI 100 100 98 96 82 79 72 28 plus: The treated plants were showered rior to the test with an amount of 15 liters per square meter within 45 minutes, and were stocked with test animals after air drying.

EXAMPLE 9 Young oak shoots having approximately equal amounts of leaves were treated with 4 milligrams of a sprayed aqueous coating of emulsions or suspension of compounds of the invention per square centimeter. The spraying was performed on a turntable in the manner described above. After drying, the shoots were stocked with 10 caterpillars (L IV stage, immediately after shedding of skins.) of the gypsy (Porthetria dispa'r L.). The animals were retained in wire quaze cages. The effects of the pesticidal compounds were determined daily, and the efiiciency was evaluated as described in Example 8. The percentage effects achieved after three days with representative compounds of the invention are listed in Table 10.

TABLE 10 Concentration of active agents, percent Percentage effect after H H H 3 L1 H I H I I l I I l I I I I I I I I I I I I I I I l I I l I I I I I I I I I I I I I l I I I l I I I I I l I l I I I I l l I l I I I I I l I I I I I l I I I l I I I I l I I l I I I I I I I I I I I I CO 0 00 o 00 0 2335 65 50 99 wn- :OHcrcnHNNmv-Nfir-LQHMHNl-Mfii-N I- IF Q o o O XIII XVI

oo' oocoocoo- I I- NUI xvn The pesticidal compounds of the invention which had not been known before were prepared in the following manner:

0.05 mole of a formamidinophenol were dissolved in a solvent such as tetrahydrofuran or in a mixture of 0.5 to 5 parts by weight of tetrahydrofuran and one part of dimethylformamide. The solution was mixed by shaking at room temperature with 0.05 mole of an alkyl or cycloalkylisocyanate. The reaction mixture was left to stand 48 hours at room temperature. Crystallization started during this time. The mixture was the heated to a boil for half an hour, and thereafter the solvent was distilled olf in a vacuum.

The residue was either recrystallized from a mixture of benzene and petroleum ether or from a mixture of tetrahydrofuran and petroleum ether. In another purification method the residue was dissolved in benzene or chloroform and passed over a chromatographic column of neutral aluminum oxide. The products obtained were oily in some cases, and were isolated either as oily liquids, or in the form of their crystallized solid salts, such as the hydrochloride, the lactate, the p-toluenesulfonate, or the chloracetate.

The following examples will illustrate the method of preparing the carbamate derivatives of the invention.

EXAMPLE 10 32.84 grams (0.2 mole) of 3-(N,N-dimethylaminomethylinimino)-phenol were dissolved in a mixture of milliliters tetrahydrofuran and 120 milliliters dimethylformamide, and the solution was left to stand 48 hours at room temperature. It Was subsequently heated to a boil for 30 minutes, and the solvent mixture was evaporated in a vacuum. The oily residue was dissolved in chloroform, and filtered over aluminum oxide (neutral). After evaporation of the chloroform in a vacuum, the residue was crystallized in the presence of a small amount of ether, and was recrystallized from ethyl acetate. The yield was 26.6 grams (60%), the melting point 102 103 C.

The elementary analysis corresponded to that of the compound C H N O Calculated (percent): C, 59.70; H, 6.83; N, 18.99. Found (percent): C, 59.88; H, 7.14; N, 19.06 which is N-methyl-3-(N,N dimethylaminomethylenimino)-phenylcarbamate.

The phenols which were employed as starting materials for preparing the pesticidal agents of the invention were prepared as follows:

0.1 mole of a suitably substituted aminophenol was dissolved either in 25 milliliters dimethylformamide or in another suitable solvent, such as acetonitrile, in the presence of 0.1 mole dimethylformamide 9.15 milliliters phosphorus oxychloride were added drop by drop with agitation while the temperature was held at or below 60 C. by means of external cooling. After completion of the phoshorus oxychloride addition, the mixture was agitated for 30 additional minutes at 60 C. When ethanol was added and the mixture was cooled to room temperature, crystallization of the desired hydrochloride usually occurred very rapidly. If necessary, crystallization was made more complete by addition of ethyl ether.

If the hydrochloride obtained was not satisfactorily pure, it was recrystallized from ethanol or from a mixture of ethanol and ether. It was then dissolved or suspended in water, and an equivalent amount of a strong base such as triethylamine, NaOH or Na CO was added whereupon the free phenol crystallized. If necessary, the aminophenol was recrystallized from a mixture of tetrahydrofuran and a light petroleum fraction.

The pesticidal compounds of the invention may also be prepared by reacting a corresponding phenol with a monosubstituted carbamic acid chloride in a manner well known in itself.

What is claimed is:

1. A compound of the formula wherein R is a radical selected from the group consisting of lower alkyl and cyclohexyl; R and R are members of the group consisting of lower alkyl radicals and R 1 1 and R together with the nitrogen atom is a heterocyclic ring selected from the group consisting of pyrollidino, piperidino and morpholino rings and R and R are members of the group consisting of hydrogen, lower alkyl radicals; lower alkenyl radicals, and halogen.

2. A compound of the formula as set forth in claim 1 and selected from the group consisting of N-methyl-4-(N', N dimethylaminomethylenimino)-3-methyl-6-isopropyl phenyl carbamate; N-methyl-4-(N,N'-diethylaminomethylenimino)-3-methyl-fi-isopropylphenyl carbamate; N- methyl-4- (N, N'-diethylaminomethylenimino -2-methyl- 5-isopropyl phenyl carbamate; N-methyl-4-(N,N'-dimethylaminomethylenimino)-3-methyl-5-isopropyl-phenyl carbamate; N'methyl-4- (N',N'-diethylaminomethylenimino 3-methyl-5-isopropyl phenyl carbamate; N-methyl-4-(N', N'-tetramethylenaminomethylenimino) 3, 5 dimethyl phenyl carbamate; N-methyl-4-(N',N'-pentamethylenaminomethylenimino)-3,S-dimethyl phenyl car-bamate; N- methyl-4-morpholinomethylenimino-3,S-dimethyl phenyl carbamate; N-methyl-3-(N,N'-dimethylaminomethylenimino)-4-methyl-phenyl carbamate; N-butyl-3-(N, N'- dimethylaminomethylenimino)-phenyl carbamate; N- methyl-2-chlor-4- (N',N'-dimethylaminomethylenimino phenyl carbamate; N-cyclohexyl-4-(N',N-dimethylarninomethylenimino)-3-methyl phenyl carbamate; N-methyl-Z, 4-dichlor-2-(N', N-dimethylaminomethylenimino)-phenyl carbamate; N-ethyl 4 (N,N'-dimethylaminomethylenimino)-phenyl carbamate; N-butyl- 4 -(N',N-dimethylaminomethylenimino)-phenyl carbamate; N-ethyl-4-(N, N-dimethylaminomethylenimino) -3,5-dimethylpheny1 carbamate; N-methyl 2 (N',N'-dimethylaminomethylenimino)-phenyl carbamate; and N-methyl-2-(N,N-dimethylaminomethylenimino -phenyl carbam ate.

3. A compound of the formula as set forth in claim 1 being N-methyl-3-(N',N'-dimethylaminomethylenimino)- phenylcarbamate.

4. A compound of the formula as set forth in claim 1 being N-methyl-4(N',N-dimethylaminomethylenimino)- phenylcarbamate.

5. A compound of the formula as set forth in claim 1 being N-methyl-4-(N,N'-dimethylaminomethylenimino)- 3-methy1 phenylcarbamate.

6. A compound of the formula as set forth in claim 1 being N-methyl-4-(N',N'-diethylaminomethylenimino)-3- methyl phenylcarbamate.

7. A compound of the formula as set forth in claim 1 being N-ethyl-4-(N,N-dimethylaminomethylenimino)-3- methyl phenylcarbamate.

8. A compound of the formula as set forth in claim 1 being N-methyl-4-(N',N-dimethylaminomethylenimino)- 2-allylphenyl carbamate.

9. A compound of the formula as set forth in claim 1 being N-methyl-4-(N,N'-dimethylaminomethylenimino)- 3,5-dimethy1-phenyl carbamate.

10. A compound of the formula as set forth in claim 1 being N-methyl-4-(N',N'-diethylamin0methylenimino)-3, S-dimethyl-phenyl carbamate.

References Cited UNITED STATES PATENTS 2,984,682 5/1961 Kaeding 260-479 JAMES A. PATTEN, Primary Examiner US. Cl. X.R. 

